Methods and compositions for improving the quality and durability of color in artificially colored hair

ABSTRACT

The present disclosure relates to compositions and methods for improving the quality and durability of color in artificially colored hair. The methods employ salts of hydroxy-polycarboxylic acids. The salts of the hydroxy-polycarboxylic acids are incorporated into a pre-color treatment composition (a composition applied to the hair prior to coloring the hair) or added directly to the coloring composition (in-color treatment composition). The salts add alkalinity to the coloring process. Hydroxy-polycarboxylic acids are incorporated into a post-color treatment composition (a composition applied to the hair after coloring the hair). The salts and the acids act as chelators, fixing the dye molecules to the hair, thereby imparting color fading resistance to the hair.

FIELD OF THE DISCLOSURE

The present disclosure relates to compositions and methods for providingcolor protection to hair, in particular, for improving the quality anddurability of color in artificially colored hair. The methods employsalts of hydroxy-polycarboxylic acids that provide alkalinity to thecoloring process. The methods also use the hydroxy-polycarboxylic acidsthemselves, which along with the salts, act as chelators.

BACKGROUND

There are many products available for changing the natural color ofhair. The process of changing the color of hair can involve eitherdepositing an artificial color onto the hair, which provides a differentshade or color to the hair, or lifting the color of the hair, such asfor example, from a dark brown shade to a medium brown or a light brownshade. Hair color can be changed using permanent, semi-permanent, ortemporary hair coloring products.

Many consumers desire a permanent color change and therefore useproducts containing permanent dyes. Conventional permanent hair coloringproducts are dye compositions comprising oxidation dye precursors, whichare also known as primary intermediates or couplers. These oxidation dyeprecursors are colorless or weakly colored compounds which, whencombined with oxidizing products, give rise to colored complexes by aprocess of oxidative condensation. The oxidizing products conventionallyuse peroxides such as hydrogen peroxide as oxidizing agents. Suchpermanent hair color products also contain ammonia or other alkalizingagents such as monoethanolamine (MEA) which causes the hair shaft toswell, thus allowing the small oxidative dye molecules to penetrate thecuticle and cortex before the oxidation condensation process iscompleted. The resulting larger-sized colored complexes from theoxidative reaction are then trapped inside the hair fiber, therebypermanently altering the color of the hair.

Newly, permanently colored hair usually has a vibrant, shiny, and richappearance. Unfortunately, however, in just a few short weeks, or insome cases even less, the color begins to fade due to washing orexposure to environmental conditions. For instance, gorgeous rich browncolors become muddy and dull, beautiful shades of blonde turn brassy,and vibrant reds do not look so vibrant anymore acquiring golden, orangeor brownish tonalities not desirable to the consumer. As describedherein, the inventors of the instant disclosure have developed methodsand kits that improve color durability by preventing color fading fromhair.

SUMMARY OF THE DISCLOSURE

The present disclosure relates to compositions and methods for improvingthe quality and durability of color in artificially colored hair. Thecompositions and methods employ salts of hydroxy-polycarboxylic acid andthe hydroxy-polycarboxylic acids themselves. The salts of thehydroxy-polycarboxylic acids are incorporated into a pre-color treatmentcomposition (a composition applied to the hair prior to coloring thehair) or added directly to the coloring composition (in-color treatmentcomposition). The salts add alkalinity to the coloring process.Hydroxy-polycarboxylic acids are incorporated into a post-colortreatment composition (a composition applied to the hair after coloringthe hair). The salts and the acids act as chelators, fixing the dyemolecules to the hair, thereby imparting color fading resistance to thehair.

In one aspect, the present disclosure relates to a method forartificially coloring hair and inhibiting the coloring from fading, themethod comprising: (a) treating hair with a pre-color treatmentcomposition comprising one or more salts of a hydroxy-polycarboxylicacid; (b) treating the hair with a coloring composition; and (c)treating the hair with a post-color treatment composition comprising oneor more hydroxy-polycarboxylic acids; wherein the hyroxy-polycarboxylicacid of the salt in (a) and in the post-color treatment of (c) has theformula

-   -   wherein, x and y are independently 0 or 1; and    -   t, u, v, and z are independently 0 to 3.

In another aspect, the present disclosure relates to a method forartificially coloring hair and inhibiting the coloring from fading, themethod comprising: (a) treating hair with a coloring compositioncomprising one or more salts of a hydroxy-polycarboxylic acid (in-colortreatment composition); and (b) treating the hair with a post-colortreatment composition comprising one or more hydroxy-polycarboxylicacids; wherein the hyroxy-polycarboxylic acid of the salt in (a) and inthe post-color treatment of (b) has the formula

-   -   wherein, x and y are independently 0 or 1; and    -   t, u, v, and z are independently 0 to 3.

The one or more salts of the hydroxy-polycarboxylic acid are typicallyalkali metal salts, alkaline earth metal salts, and/or transition metalsalts. Non-limiting examples of salts of the hydroxy-polycarboxylic acidinclude salts of citric acid, tartaric acid, malic acid, 2-hydroxymalonic acid, 2-hydroxyl n-butyl 1,2,4-tricarboxylic acid, glucaricacid, and/or 2-hydroxy n-butyl 1,3,4-tricarboxylic acid. Similarly,non-limiting examples of the hydroxy-polycarboxylic acids include citricacid, tartaric acid, malic acid, 2-hydroxy malonic acid, 2-hydroxyln-butyl 1,2,4-tricarboxylic acid, glucaric acid, and 2-hydroxy n-butyl1,3,4-tricarboxylic acid.

Finally, the instant disclosure relates to kits comprising the variouscompositions used to carry out the methods described herein (e.g.,pre-color treatment compositions, coloring compositions, and post-colortreatment compositions). The kits may be used by hair-care professionalsand salons for treating the hair of patrons or the kits may be purchasedand used at home directly by consumers.

DETAILED DESCRIPTION OF THE DISCLOSURE

The present disclosure relates to improving the quality and durabilityof the color in artificially colored hair. The methods described hereinemploy salts of hydroxy-polycarboxylic acids and thehydroxy-polycarboxylic acids themselves. When both of these componentsare used, color quality and color durability are improved such thatcolor fading is minimized or inhibited.

In one aspect, the present disclosure relates to a method forartificially coloring hair and inhibiting the coloring from fading, themethod comprising: (a) treating hair with a pre-color treatmentcomposition comprising one or more salts of a hydroxy-polycarboxylicacid; (b) treating the hair with a coloring composition; and (c)treating the hair with a post-color treatment composition comprising oneor more hydroxy-polycarboxylic acids; wherein the hyroxy-polycarboxylicacid of the salt in (a) and in the post-color treatment of (c) has theformula

-   -   wherein, x and y are independently 0 or 1; and    -   t, u, v, and z are independently 0 to 3.

In another aspect, the present disclosure relates to a method forartificially coloring hair and inhibiting the coloring from fading, themethod comprising: (a) treating hair with a coloring compositioncomprising one or more salts of a hydroxy-polycarboxylic acid (in-colortreatment composition); and (b) treating the hair with a post-colortreatment composition comprising one or more hydroxy-polycarboxylicacids; wherein the hyroxy-polycarboxylic acid of the salt in (a) and inthe post-color treatment of (b) has the formula

-   -   wherein, x and y are independently 0 or 1; and    -   t, u, v, and z are independently 0 to 3.

The one or more salts of the hydroxy-polycarboxylic acid are typicallyalkali metal salts, alkaline earth metal salts, and/or transition metalsalts. Non-limiting examples of salts of the hydroxy-polycarboxylic acidinclude salts of citric acid, tartaric acid, malic acid, 2-hydroxymalonic acid, 2-hydroxyl n-butyl 1,2,4-tricarboxylic acid, glucaricacid, and/or 2-hydroxy n-butyl 1,3,4-tricarboxylic acid. In some cases,salts of citric acid, such as trisodium citrate, are used.

Non-limiting examples of the hydroxy-polycarboxylic acids include citricacid, tartaric acid, malic acid, 2-hydroxy malonic acid, 2-hydroxyln-butyl 1,2,4-tricarboxylic acid, glucaric acid, and 2-hydroxy n-butyl1,3,4-tricarboxylic acid. In some cases, the hydroxy-polycarboxylic acidis citric acid.

The total amount of the one or more salts of the hydroxy-polycarboxylicacid, when used in a pre-color treatment composition, is about 1 wt. %to about 75 wt. %, based on the total weight of the pre-color treatmentcomposition. The total amount of the one more salts may be from about 1wt. % to about 25 wt. %, about 30 wt. %, about 35 wt. %, about 40 wt. %,about 45 wt. %, about 50 wt. %, about 55 wt. %, about 60 wt. %, about 65wt. %, or about 70 wt. %. The total amount of the one more salts may befrom about 5 wt. % to about 25 wt. %, about 30 wt. %, about 35 wt. %,about 40 wt. %, about 45 wt. %, about 50 wt. %, about 55 wt. %, about 60wt. %, about 65 wt. %, or about 70 wt. %. The total amount of the onemore salts may be from about 10 wt. % to about 25 wt. %, about 30 wt. %,about 35 wt. %, about 40 wt. %, about 45 wt. %, about 50 wt. %, about 55wt. %, about 60 wt. %, about 65 wt. %, or about 70 wt. %. The totalamount of the one more salts may be from about 15 wt. % to about 25 wt.%, about 30 wt. %, about 35 wt. %, about 40 wt. %, about 45 wt. %, about50 wt. %, about 55 wt. %, about 60 wt. %, about 65 wt. %, or about 70wt. %. The total amount of the one more salts may be from about 20 wt. %to about 40 wt. %, about 45 wt. %, about 50 wt. %, about 55 wt. %, about60 wt. %, about 65 wt. %, or about 70 wt. %. The total amount of the onemore salts may be from about 25 wt. % to about 40 wt. %, about 45 wt. %,about 50 wt. %, about 55 wt. %, about 60 wt. %, about 65 wt. %, or about70 wt. %. The total amount of the one more salts may be from about 30wt. % to about 45 wt. %, about 50 wt. %, about 55 wt. %, about 60 wt. %,about 65 wt. %, or about 70 wt. %.

The total amount of the one or more salts of the hydroxy-polycarboxylicacid, when used in a coloring composition, is about 1 wt. % to about 50wt. %, based on the total weight of the coloring composition. The totalamount of the one or more salts may be from about 1 wt. % to about 15wt. %, about 20 wt. %, about 25 wt. %, about 30 wt. %, about 35 wt. %,about 40 wt. %, about 45 wt. %, or about 50 wt. %. The total amount ofthe one or more salts may be from about 5 wt. % to about 20 wt. %, about25 wt. %, about 30 wt. %, about 35 wt. %, about 40 wt. %, about 45 wt.%, or about 50 wt. %. The total amount of the one or more salts may befrom about 10 wt. % to about 25 wt. %, about 30 wt. %, about 35 wt. %,about 40 wt. %, about 45 wt. %, or about 50 wt. %. The total amount ofthe one or more salts may be from about 15 wt. % to about 30 wt. %,about 35 wt. %, about 40 wt. %, about 45 wt. %, or about 50 wt. %. Thetotal amount of the one or more salts may be from about 20 wt. % toabout 40 wt. %, about 45 wt. %, or about 50 wt. %.

The total amount of the one or more hydroxy-polycarboxylic acids in thepost-color treatment composition, is about 1 wt. % to about 75 wt. %,based on the total weight of the post-color treatment composition. Thetotal amount of the one more acids may be from about 1 wt. % to about 25wt. %, about 30 wt. %, about 35 wt. %, about 40 wt. %, about 45 wt. %,about 50 wt. %, about 55 wt. %, about 60 wt. %, about 65 wt. %, or about70 wt. %. The total amount of the one more acids may be from about 5 wt.% to about 25 wt. %, about 30 wt. %, about 35 wt. %, about 40 wt. %,about 45 wt. %, about 50 wt. %, about 55 wt. %, about 60 wt. %, about 65wt. %, or about 70 wt. %. The total amount of the one more acids may befrom about 10 wt. % to about 25 wt. %, about 30 wt. %, about 35 wt. %,about 40 wt. %, about 45 wt. %, about 50 wt. %, about 55 wt. %, about 60wt. %, about 65 wt. %, or about 70 wt. %. The total amount of the onemore acids may be from about 15 wt. % to about 25 wt. %, about 30 wt. %,about 35 wt. %, about 40 wt. %, about 45 wt. %, about 50 wt. %, about 55wt. %, about 60 wt. %, about 65 wt. %, or about 70 wt. %. The totalamount of the one more acids may be from about 20 wt. % to about 40 wt.%, about 45 wt. %, about 50 wt. %, about 55 wt. %, about 60 wt. %, about65 wt. %, or about 70 wt. %. The total amount of the one more acids maybe from about 25 wt. % to about 40 wt. %, about 45 wt. %, about 50 wt.%, about 55 wt. %, about 60 wt. %, about 65 wt. %, or about 70 wt. %.The total amount of the one more acids may be from about 30 wt. % toabout 45 wt. %, about 50 wt. %, about 55 wt. %, about 60 wt. %, about 65wt. %, or about 70 wt. %.

The pre-color treatment compositions described herein are applied to thehair before applying the coloring composition. The pre-color treatmentcompositions are applied to the hair in a sufficient amount to cover thehair and are allowed to remain on the hair for a period of time. Thepre-color treatment compositions are typically applied to the hair atroom temperature (about 15° C. to about 25° C.) and allowed to at leastbriefly remain on the hair. For example, the pre-color treatmentcompositions may be allowed to remain on the hair for at least about 1,about 2, about 5, about 10, about 15, about 20, about 25, or about 30minutes after application, or up to about 1 or about 2 hours, until thehair is subsequently colored. Further, the pre-treatment composition maybe applied and allowed to remain on the hair for 1 to 30 minutes at roomtemperature (about 15° C. to about 25° C.). The post-color treatmentcompositions may be applied at higher temperatures, for example, attemperatures from about 20° C. to about 45° C., about 25° C. to about45° C., about 30° C. to about 45° C. The compositions may be applied tothe hair at one temperature, and then the hair containing thecompositions may be warmed during treatment. Further, post-colortreatment composition may be applied to the hair, and allowed tonaturally dry on the hair, or a drying step may be included using heatand/or air (e.g., blow drying) to dry the composition onto the hair.

The pre-color treatment compositions may be applied to dry hair andallowed to remain on the hair for sufficient amount of time to absorbthroughout the hair, and may optionally be dried onto the hair. Forexample, the hair may be blown dry after application of the pre-colortreatment composition. The pre-color treatment composition may or maynot be removed, e.g., by shampooing, prior to application of a coloringcomposition.

The coloring compositions described herein are applied to the hair afterapplication of a pre-color treatment composition in cases where apre-color treatment composition is employed (as described above). Thecoloring compositions are allowed to remain on the hair for a sufficientamount of time to adequately color the hair, as is well known in theart. For example, the coloring composition may be allowed to remain onthe hair for 1 to 60 minutes at a temperature of 20 to 45° C. Typically,the coloring composition is allowed to remain on the hair for at leastabout 1 min., about 2 min., about 5 min., about 10 min., about 15 min.,about 20 min., about 25 min., about 30 min. and may remain on the hairfor up to about 1 hour, 1.5 hours, 2 hours, or longer. The amount oftime that the coloring composition is allowed to remain on the hairoften depends on the strength of the coloring composition, the originalcolor and strength of the hair being colored, and the degree of colorchange desired. The coloring compositions may optionally be warmed uponapplication to the hair, for example, from a temperature of about 25°C., about 30° C., about 35° C., or higher, up to a temperature of about40° C., or higher. The warming may expedite the coloring process.Typically, after the coloring process is complete, the coloringcomposition is removed, for example, by shampooing, prior to applicationof a post-color treatment composition (in situations where a post-colortreatment composition is applied). The colored hair may optionally bedried prior to application of a post-color treatment composition.

Typically, the post-color treatment composition is applied to the hairafter the hair is colored, e.g., within 24 hours. Often, the post-colortreatment composition is applied to the hair immediately afterartificially coloring the hair, for example, within about 1 min., about5 min., about 10 min., about 15 min., about 30 min., about 1 hour, orabout 2 hours after artificially coloring the hair. The post-colortreatment compositions described herein may be applied once, or may beapplied multiple times. For example, the post-color treatmentcompositions may be applied daily, weekly, monthly, or applied duringthe time of washing the hair. The post-color treatment compositions maybe “stand-alone” products or may be formulated as another cosmeticproduct that is applied to the hair, thereby creating a multi-purposeproduct. For example, the post-color treatment compositions may beformulated as a pre- or post-shampooing treatment or “rinse” product, itmay be formulated as a conditioner, which is typically applied to thehair immediately after shampooing. It may be formulated as an“overnight” treatment to be applied to the hair and allowed to remain onthe hair while the consumer sleeps.

The post-color treatment compositions may be applied to the hair at roomtemperature (about 15° C. to about 25° C.). Further, the post-colortreatment compositions may be applied at higher temperatures, forexample, at temperatures from about 20° C. to about 45° C., about 25° C.to about 45° C., about 30° C. to about 45° C. The compositions may beapplied to the hair at one temperature, and then the hair containing thecompositions may be warmed during treatment. Further, post-colortreatment composition may be applied to the hair, and allowed tonaturally dry on the hair, or a drying step may be included using heatand/or air (e.g., blow drying) to dry the composition onto the hair.

The coloring compositions of the present disclosure typically compriseat least one colorant compound chosen from oxidative dye precursors,direct dyes, pigments, and mixtures thereof. The oxidation dyes aregenerally chosen from one or more oxidation bases optionally combinedwith one or more couplers. The coloring composition may include anoxidation agent. In many cases an oxidative agent is combined with thecoloring compositions immediately prior to treating hair with thecoloring treatment.

Finally, the instant disclosure relates to kits comprising thecompositions described herein, including the pre-color treatmentcompositions, the coloring compositions and the post-color treatmentcompositions. Each of the kits may also optionally include an oxidizingagent or a composition comprising an oxidizing agent. Often, the kitsdescribed herein are accompanied by instructions for use, and may alsooptionally include utensils for mixing, applying, and maintaining thecompositions.

More exhaustive but non-limiting lists of components useful in thecompositions disclosed herein are presented below.

Cosmetically Acceptable Solvent (or Carrier)

The compositions of the present disclosure may be presented in acosmetically acceptable solvent. This cosmetically acceptable solventmay include, for example, water or a mixture of water and at least onecosmetically acceptable organic solvent.

As examples of organic solvents, non-limiting mentions can be made ofmonoalcohols and polyols such as ethyl alcohol, isopropyl alcohol,propyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols orglycol ethers such as, for example, monomethyl, monoethyl and monobutylethers of ethylene glycol, propylene glycol or ethers thereof such as,for example, monomethyl ether of propylene glycol, butylene glycol,hexylene glycol, dipropylene glycol as well as alkyl ethers ofdiethylene glycol, for example monoethyl ether or monobutyl ether ofdiethylene glycol.

Other suitable examples of organic solvents are ethylene glycol,propylene glycol, butylene glycol, hexylene glycol, propane diol, andglycerin.

The organic solvents for use in the present disclosure can be volatileor non-volatile compounds.

The cosmetically acceptable solvent may be employed according to thepresent disclosure in an amount ranging from about 5% to about 95% byweight, or such as from about 20% to about 90% by weight, such as fromabout 30 to about 80% by weight, or such as from about 35% to about 75%by weight, such as from about 5 to about 50% by weight, such as fromabout 50 to 95% by weight, based on the total weight of the composition.

The organic solvent may be employed according to the present disclosurein an amount ranging from about 0.1% to about 25% by weight, such asfrom about 1% to about 15% by weight, or such as from about 3% to about10% by weight, or such as from about 5% to about 10% by weight, based onthe total weight of the disclosure composition of the presentdisclosure.

Colorants

The coloring compositions of the present disclosure include at least onecolorant compound chosen from oxidative dye precursors, direct dyes,pigments, and mixtures thereof. The oxidation dyes are generally chosenfrom one or more oxidation bases optionally combined with one or morecouplers. By way of example, the oxidation bases are chosen frompara-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols,ortho-aminophenols and heterocyclic bases, and the addition saltsthereof.

Among the para-phenylenediamines that may be mentioned, for example, arepara-phenylenediamine, para-toluenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,4-N,N-bis(.beta.-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(.beta.-hydroxyethyl)amino-2-chloroaniline,2-.beta.-hydroxyethyl-para-phenylenediamine,2-methoxymethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(.beta.-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N-ethyl-N-(.beta.-hydroxyethyl)-para-phenylenediamine,N-(.beta.,.gamma.-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-.beta.-hydroxyethyloxy-para-phenylenediamine,2-.beta.-acetylaminoethyloxy-para-phenylenediamine,N-(.beta.-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine,2-thienyl-para-phenylenediamine,2-.beta.-hydroxyethylamino-5-aminotoluene and3-hydroxy-1-(4′-aminophenyl)pyrrolidine, and the addition salts thereofwith an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine,para-toluenediamine, 2-isopropyl-para-phenylenediamine,2-.beta.-hydroxyethyl-para-phenylenediamine,2-.beta.-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine and2-.beta.-acetylaminoethyloxy-para-phenylenediamine, and the additionsalts thereof with an acid, are particularly preferred.

Among the bis(phenyl)alkylenediamines that may be mentioned, forexample, areN,N′-bis(.beta.-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropano-1,N,N′-bis(.beta.-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(.beta.-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamin-e,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the addition saltsthereof.

Among the para-aminophenols that may be mentioned, for example, arepara-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol,4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(.beta.-hydroxyethylaminomethyl)phenol and4-amino-2-fluorophenol, and the addition salts thereof with an acid.

Among the ortho-aminophenols that may be mentioned, for example, are2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and5-acetamido-2-aminophenol, and the addition salts thereof.

Among the heterocyclic bases that may be mentioned, for example, arepyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives that may be mentioned are the compoundssuch as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridineand 3,4-diaminopyridine, and the addition salts thereof. Other pyridineoxidation bases that are useful in the present disclosure are the3-aminopyrazolo[1,5-a]pyridine oxidation bases or the addition saltsthereof described, for example, in patent application FR 2 801 308.Examples that may be mentioned include pyrazolo[1,5-a]pyrid-3-ylamine,2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine,2-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine,3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid,2-methoxypyrazolo[1,5-a]pyrid-3-ylamine,(3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol,2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol,2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol,(3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol,3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine,pyrazolo[1,5-a]pyridine-3,7-diamine,7-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine,pyrazolo[1,5-a]pyridine-3,5-diamine,5-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine,2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol,2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol,3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol,3-aminopyrazolo[1,5-a]pyridin-6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-ol,2-.quadrature.-hydroxyethoxy-3-amino-pyrazolo[1,5-a]pyridine;2-(4-dimethylpyperazinium-1-yl)-3-amino-pyrazolo[1,5-a]pyridine; and theaddition salts thereof.

More particularly oxidation bases that are useful in the presentdisclosure are selected from 3-aminopyrazolo-[1,5-a]-pyridines andpreferably substituted on carbon atom 2 by:

(a) one (di)(C₁-C₆)(alkyl)amino group wherein said alkyl group can besubstituted by at least one hydroxy, amino, imidazolium group;

(b) one heterocycloalkyl group containing from 5 to 7 members chain, andfrom 1 to 3 heteroatoms, potentially cationic, potentially substitutedby one or more (C₁-C₆-alkyl, such as di(C1-C4)alkylpiperazinium; or

(c) one (C₁-C₆)alkoxy potentially substituted by one or more hydroxygroups such as .quadrature.-hydroxyalkoxy, and the addition saltsthereof.

Among the pyrimidine derivatives that may be mentioned are compoundssuch as 2,4,5,6-tetraaminopyrimidine,4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and theiraddition salts and their tautomeric forms, when a tautomeric equilibriumexists.

Among the pyrazole derivatives that may be mentioned are compounds suchas 4,5-diamino-1-methyl-pyrazole,4,5-diamino-1-(.beta.-hydroxyethyl)pyrazole, 3,4-diamino-pyrazole,4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethylpyrazole,4,5-diamino-3-methyl-1-phenyl-pyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methyl-pyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(.beta.-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methyl-pyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole,3,5-diamino-4-(.beta.-hydroxyethyl)amino-1-methylpyrazole, and theaddition salts thereof. 4,5-Diamino-1-(.beta.-methoxyethyl)pyrazole mayalso be used.

Pyrazole derivatives that may also be mentioned includediamino-N,N-dihydropyrazolopyrazolones such as the following compoundsand the addition salts thereof:2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-on-e,4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-di-(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol--1-one,2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1--one,2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one,4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one,4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol--3-one,2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-o-ne.2,3-Diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a saltthereof will preferably be used.4,5-Diamino-1-(.beta.-hydroxyethyl)pyrazole and/or2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a saltthereof will preferentially be used as heterocyclic bases.

Composition according to the present disclosure may optionally compriseone or more couplers advantageously chosen from those conventionallyused in the dyeing or coloring of keratin fibers.

Among these couplers, mention may be made especially ofmeta-phenylenediamines, meta-aminophenols, meta-diphenols,naphthalene-based couplers and heterocyclic couplers, and also theaddition salts thereof.

Mention may be made, for example, of 2-methyl-5-aminophenol,5-N-(.beta.-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,5-amino-6-chloro-o-cresol (3-amino-2-chloro-6-methylphenol),1,3-dihydroxybenzene, 1,3-dihydroxy-2-methyl-benzene,4-chloro-1,3-dihydroxybenzene,2,4-diamino-1-(.beta.-hydroxyethyloxy)benzene,2-amino-4-(.beta.-hydroxyethylamino)-1-methoxybenzene,1,3-diaminobenzene, 1,3-bis(2,4-diamino-phenoxy)propane,3-ureidoaniline, 3-ureido-1-dimethylamino-benzene, sesamol,1-.beta.-hydroxyethylamino-3,4-methylene-dioxybenzene, .alpha.-naphthol,2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole,4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine,6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine,1-N-(.beta.-hydroxyethyl)amino-3,4-methylene-dioxybenzene,2,6-bis(J-hydroxyethylamino)toluene, 6-hydroxy-indoline,2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one,1-phenyl-3-methylpyrazol-5-one,2,6-dimethyl-pyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole and6-methylpyrazolo[1,5-a]benzimidazole, the addition salts thereof with anacid, and mixtures thereof.

In general, the addition salts of the oxidation bases and couplers thatmay be used in the context of the disclosure are especially selectedfrom the addition salts with an acid such as the hydrochlorides,hydrobromides, sulfates, citrates, succinates, tartrates, lactates,tosylates, benzenesulfonates, phosphates and acetates.

The oxidation base(s) each advantageously represent from 0.001% to 10%by weight relative to the total weight of the composition, andpreferably from 0.005% to 5% by weight relative to the total weight ofthe compositions of the present disclosure.

The coupler(s), if they are present, each advantageously represent from0.001% to 10% by weight relative to the total weight of the composition,and preferably from 0.005% to 5% by weight relative to the total weightof the compositions of the present disclosure.

Compositions according to the disclosure may optionally comprise b) oneor more synthetic or natural direct dyes, chosen from anionic andnonionic species, preferably cationic or nonionic species, either assole dyes or in addition to the oxidation dye(s).

Examples of suitable direct dyes that may be mentioned include azodirect dyes; (poly)methine dyes such as cyanins, hemicyanins andstyryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes;tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanin dyes, andnatural direct dyes, alone or as mixtures.

Many direct dyes are cationic direct dyes. Mention may be made of thehydrazono cationic dyes of formulas (Va) and (V′a), the azo cationicdyes (VIa) and (VI′a) and the diazo cationic dyes (VIIa) below:Het⁺-C(R^(a))═N—N(R^(b))—Ar,An ⁻  (Va)Het⁺-N(R^(a))—N═C(R^(b))—Ar,An ⁻  (V′a)Het⁺-N═N—Ar,An ⁻  (VIa)Ar⁺—N═N—Ar″,An ⁻  (VI′a) andHet ⁺-N═N—Ar′—N═N—Ar,An ⁻  (VIIa)

-   -   in which formulas (Va), (V′a), (VIa), (VI′a) and (VIIa):    -   Het⁺ represents a cationic heteroaryl radical, preferably        bearing an endocyclic cationic charge, such as imidazolium,        indolium or pyridinium, optionally substituted preferentially        with one or more (C₁-C₈ alkyl groups such as methyl;    -   Ar⁺ representing an aryl radical, such as phenyl or naphthyl,        bearing an exocyclic cationic charge, preferentially ammonium,        particularly tri(C₁-C₈)alkylammonium such as trimethylammonium;    -   Ar represents an aryl group, especially phenyl, which is        optionally substituted, preferentially with one or more        electron-donating groups such as i) optionally substituted        (C₁-C₈)alkyl, ii) optionally substituted (C₁-C₈)alkoxy, iii)        (di)(C₁-C₈)(alkyl)amino optionally substituted on the alkyl        group(s) with a hydroxyl group, iv) aryl(C₁-C₈)alkylamino, v)        optionally substituted N—(C₁-C₈)alkyl-N-aryl(C₁-C₈)alkylamino or        alternatively Ar represents a julolidine group;    -   Ar′ is an optionally substituted divalent (hetero)arylene group        such as phenylene, particularly para-phenylene, or naphthalene,        which are optionally substituted, preferentially with one or        more groups (C₁-C₈)alkyl, hydroxyl or (C₁-C₈)alkoxy    -   Ar″ is an optionally substituted (hetero)aryl group such as        phenyl or pyrazolyl, which are optionally substituted,        preferentially with one or more groups (C₁-C₈)alkyl, hydroxyl,        (di)(C₁-C₈)(alkyl)amino, (C₁-C₈)alkoxy or phenyl;    -   R^(a) and R^(b), which may be identical or different, represent        a hydrogen atom or a group (C₁-C₈)alkyl, which is optionally        substituted, preferentially with a hydroxyl group;    -   or alternatively the substituent R^(a) with a substituent of        Het⁺ and/or R_(b) with a substituent of Ar and/or R^(a) with        R_(b) form, together with the atoms that bear them, a        (hetero)cycloalkyl;    -   particularly, R^(a) and R_(b) represent a hydrogen atom or a        group (C₁-C₄)alkyl, which is optionally substituted with a        hydroxyl group;    -   An⁻ represents an anionic counter-ion such as mesylate or        halide. In particular, mention may be made of the azo and        hydrazono cationic dyes bearing an endocyclic cationic charge of        formulae (Va), (V′a) and (VIa) as defined previously. More        particularly those of formulae (Va), (V′a) and (VIa) derived        from the dyes described in patent applications WO 95/15144, WO        95/01772 and EP-714954, which are incorporated herein by        reference in their entirety.

In some cases, the cationic part is derived from the followingderivatives:

-   -   formulae (V-1) and (VI-1) with:    -   R¹ representing a (C₁-C₄) alkyl group such as methyl;    -   R² and R³, which are identical or different, represent a        hydrogen atom or a (C₁-C₄)alkyl group, such as methyl; and    -   R⁴ represents a hydrogen atom or an electron-donating group such        as optionally substituted (C₁-C₈)alkyl, optionally substituted        (C₁-C₈)alkoxy, or (di)(C₁-C₈)(alkyl)amino optionally substituted        on the alkyl group(s) with a hydroxyl group; particularly, R⁴ is        a hydrogen atom,    -   Z represents a CH group or a nitrogen atom, preferentially CH;    -   An⁻ represents an anionic counter-ion such as mesylate or        halide.

Particularly, the dye of formulae (Va-1) and (VIa-1) is chosen fromBasic Red 51, Basic Yellow 87 and Basic Orange 31 or derivativesthereof:

Among the natural direct dyes that may be used according to thedisclosure, mention may be made of lawsone, juglone, alizarin, purpurin,carminic acid, kermesic acid, purpurogallin, protocatechaldehyde,indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Extractsor decoctions containing these natural dyes and in particularhenna-based poultices or extracts may also be used.

When they are present, the direct dye(s) more particularly representfrom 0.001% to 10% by weight and preferably from 0.005% to 5% by weightof the total weight of the compositions of the present disclosure.

Surfactants

The various compositions described herein may include one or moresurfactants, including cationic, anionic, non-ionic and/oramphoteric/zwitterionic surfactants. Non-limiting examples ofsurfactants that may be used are provided below.

Cationic Surfactants

The term “cationic surfactant” means a surfactant that is positivelycharged when it is contained in the composition according to thedisclosure. This surfactant may bear one or more positive permanentcharges or may contain one or more functions that are cationizable inthe composition according to the disclosure.

Non-limiting examples of cationic surfactants include behenalkoniumchloride, benzethonium chloride, cetylpyridinium chloride,behentrimonium chloride, lauralkonium chloride, cetalkonium chloride,cetrimonium bromide, cetrimonium chloride, cethylamine hydrofluoride,chlorallylmethenamine chloride (Quaternium-15), distearyldimoniumchloride (Quaternium-5), dodecyl dimethyl ethylbenzyl ammonium chloride(Quaternium-14), Quaternium-22, Quaternium-26, Quaternium-18 hectorite,dimethylaminoethylchloride hydrochloride, cysteine hydrochloride,diethanolammonium POE (10) oletyl ether phosphate, diethanolammonium POE(3)oleyl ether phosphate, tallow alkonium chloride, dimethyldioctadecylammoniumbentonite, stearalkonium chloride, domiphen bromide,denatonium benzoate, myristalkonium chloride, laurtrimonium chloride,ethylenediamine dihydrochloride, guanidine hydrochloride, pyridoxineHCl, iofetamine hydrochloride, meglumine hydrochloride,methylbenzethonium chloride, myrtrimonium bromide, oleyltrimoniumchloride, polyquaternium-1, procainehydrochloride, cocobetaine,stearalkonium bentonite, stearalkoniumhectonite, stearyl trihydroxyethylpropylenediamine dihydrofluoride, tallowtrimonium chloride, andhexadecyltrimethyl ammonium bromide.

The cationic surfactant(s) may be chosen from optionallypolyoxyalkylenated, primary, secondary or tertiary fatty amines, orsalts thereof, and quaternary ammonium salts, and mixtures thereof.

The fatty amines generally comprise at least one C₈-C₃₀hydrocarbon-based chain.

Examples of quaternary ammonium salts that may especially be mentionedinclude: those corresponding to the general formula (III) below:

in which the groups R₈ to R₁₁, which may be identical or different,represent a linear or branched, saturated or unsaturated aliphatic groupcomprising from 1 to 30 carbon atoms, or an aromatic group such as arylor alkylaryl, at least one of the groups R₈ to R₁₁ denoting a groupcomprising from 8 to 30 carbon atoms and preferably from 12 to 24 carbonatoms. The aliphatic groups may comprise heteroatoms especially such asoxygen, nitrogen, sulfur and halogens. The aliphatic groups are chosen,for example, from C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₁-C₃₀ alkoxy,polyoxy(C₂-C₆)alkylene, C₁-C₃₀ alkylamide,(C₁₂-C₂₂)alkylamido(C₂-C₆)alkyl, (C₁₂-C₂₂)alkyl acetate and C₁-C₃₀hydroxyalkyl groups; X⁻ is an anion chosen from the group of halides,phosphates, acetates, lactates, (C₁-C₄)alkyl sulfates, and (C₁-C₄)alkyl-or (C₁-C₄)alkylarylsulfonates.

Among the quaternary ammonium salts of formula (III), those that arepreferred are, on the one hand, tetraalkylammonium salts, for instancedialkyldimethylammonium or alkyltrimethylammonium salts in which thealkyl group contains approximately from 12 to 22 carbon atoms, inparticular behenyltrimethylammonium, distearyldimethylammonium,cetyltrimethylammonium or benzyldimethylstearylammonium salts, or, onthe other hand, oleocetyldimethylhydroxyethylammonium salts,palmitylamidopropyltrimethylammonium salts,stearamidopropyltrimethylammonium salts andstearamidopropyldimethylcetearylammonium salts.

In some cases it is useful to use salts such as the chloride salts ofthe following compounds:

A. a quaternary ammonium salt of imidazoline, such as, for example,those of formula (IV) below:

in which R₁₂ represents an alkenyl or alkyl group comprising from 8 to30 carbon atoms, derived for example from tallow fatty acids, R₁₃represents a hydrogen atom, a C₁-C₄ alkyl group or an alkyl or alkenylgroup comprising from 8 to 30 carbon atoms, R₁₄ represents a C₁-C₄ alkylgroup, R₁₅ represents a hydrogen atom or a C₁-C₄ alkyl group, X⁻ is ananion chosen from the group of halides, phosphates, acetates, lactates,alkyl sulfates, alkyl- or alkylaryl-sulfonates in which the alkyl andaryl groups preferably comprise, respectively, from 1 to 20 carbon atomsand from 6 to 30 carbon atoms. R₁₂ and R₁₃ preferably denote a mixtureof alkenyl or alkyl groups containing from 12 to 21 carbon atoms,derived for example from tallow fatty acids, R₁₄ preferably denotes amethyl group, and R₁₅ preferably denotes a hydrogen atom. Such a productis sold, for example, under the name Rewoquat® W 75 by the company Rewo;

B. a quaternary diammonium or triammonium salt, in particular of formula(V):

in which R₁₆ denotes an alkyl radical comprising approximately from 16to 30 carbon atoms, which is optionally hydroxylated and/or interruptedwith one or more oxygen atoms, R₁₇ is chosen from hydrogen or an alkylradical comprising from 1 to 4 carbon atoms or a group(R_(16a))(R_(17a))(R_(18a))N—(CH₂)₃,

R_(16a), R_(17a), R_(18a), R₁₈, R₁₉, R₂₀ and R₂₁, which may be identicalor different, being chosen from hydrogen and an alkyl radical comprisingfrom 1 to 4 carbon atoms, and X⁻ is an anion chosen from the group ofhalides, acetates, phosphates, nitrates and methyl sulfates. Suchcompounds are, for example, Finquat CT-P, sold by the company Finetex(Quaternium 89), and Finquat CT, sold by the company Finetex (Quaternium75),

C. a quaternary ammonium salt containing at least one ester function,such as those of formula (VI) below:

in which:

R₂₂ is chosen from C₁-C₆ alkyl groups and C₁-C₆ hydroxyalkyl ordihydroxyalkyl groups;

R₂₃ is chosen from:

R₂₇, which is a linear or branched, saturated or unsaturated C₁-C₂₂hydrocarbon-based group, and a hydrogen atom,

R₂₅ is chosen from:

R₂₉, which is a linear or branched, saturated or unsaturated C₁-C₆hydrocarbon-based group, and a hydrogen atom,

R₂₄, R₂₆ and R₂₈, which may be identical or different, are chosen fromlinear or branched, saturated or unsaturated C₇-C₂₁ hydrocarbon-basedgroups;

r, s and t, which may be identical or different, are integers rangingfrom 2 to 6;

y is an integer ranging from 1 to 10;

x and z, which may be identical or different, are integers ranging from0 to 10;

X⁻ is a simple or complex, organic or mineral anion;

with the proviso that the sum x+y+z is from 1 to 15, that when x is 0then R_(n) denotes R₂₇, and that when z is 0 then R₂₅ denotes R₂₉.

The alkyl groups R₂₂ may be linear or branched, and more particularlylinear. In some cases, R₂₂ denotes a methyl, ethyl, hydroxyethyl ordihydroxypropyl group, and more particularly a methyl or ethyl group.Advantageously, the sum x+y+z is from 1 to 10.

When R₂₃ is a hydrocarbon-based group R₂₇, it may be long and containfrom 12 to 22 carbon atoms, or may be short and contain from 1 to 3carbon atoms. When R₂₅ is an R₂₉ hydrocarbon-based group, it preferablycontains 1 to 3 carbon atoms. Advantageously, R₂₄, R₂₆ and R₂₈, whichmay be identical or different, are chosen from linear or branched,saturated or unsaturated C₁₁-C₂₁ hydrocarbon-based groups, and moreparticularly from linear or branched, saturated or unsaturated C₁₁-C₂₁alkyl and alkenyl groups.

In some cases, x and z, which may be identical or different, have valuesof 0 or 1. Likewise, in some cases y is equal to 1. In some cases, r, sand t, which may be identical or different, are equal to 2 or 3, andeven more particularly are equal to 2.

The anion X⁻ is may be a halide (chloride, bromide or iodide) or analkyl sulfate, more particularly methyl sulfate. However, use may bemade of methanesulfonate, phosphate, nitrate, tosylate, an anion derivedfrom an organic acid, such as acetate or lactate, or any other anioncompatible with the ammonium containing an ester function.

The anion X⁻ is even more particularly chloride or methyl sulfate.

Use is made more particularly, in the composition according to theinvention, of the ammonium salts of formula (VI) in which:

R₂₂ denotes a methyl or ethyl group,

x and y are equal to 1;

z is equal to 0 or 1;

r, s and t are equal to 2;

R₂₃ is chosen from:

methyl, ethyl or C₁₄-C₂₂ hydrocarbon-based groups, and a hydrogen atom;

R₂₅ is chosen from:

and a hydrogen atom;

R₂₄, R₂₆ and R₂₈, which may be identical or different, are chosen fromlinear or branched, saturated or unsaturated C₁₃-C₁₇ hydrocarbon-basedgroups, and preferably from linear or branched, saturated or unsaturatedC₁₃-C₁₇ alkyl and alkenyl groups. The hydrocarbon-based groups areadvantageously linear.

Mention may be made, for example, of the compounds of formula (VI) suchas the diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium,monoacyloxyethyldihydroxyethylmethylammonium,triacyloxyethylmethylammonium andmonoacyloxyethylhydroxyethyldimethylammonium salts (chloride or methylsulfate in particular), and mixtures thereof. The acyl groups preferablycontain 14 to 18 carbon atoms and are obtained more particularly from aplant oil, such as palm oil or sunflower oil. When the compound containsseveral acyl groups, these groups may be identical or different.

These products are obtained, for example, by direct esterification oftriethanolamine, triisopropanolamine, an alkyldiethanolamine or analkyldiisopropanolamine, which are optionally oxyalkylenated, withC₁₀-C₃₀ fatty acids or with mixtures of C₁₀-C₃₀ fatty acids of plant oranimal origin, or by transesterification of the methyl esters thereof.This esterification is followed by quaternization using an alkylatingagent such as an alkyl (preferably methyl or ethyl) halide, a dialkyl(preferably methyl or ethyl) sulfate, methyl methanesulfonate, methylpara-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.Such compounds are, for example, sold under the names Dehyquart® by thecompany Henkel, Stepanquat® by the company Stepan, Noxamium® by thecompany Ceca or Rewoquat® WE 18 by the company Rewo-Witco.

The composition according to the invention may contain, for example, amixture of quaternary ammonium monoester, diester and triester saltswith a weight majority of diester salts.

Use may be made of behenoylhydroxypropyltrimethylammonium chloride,provided by Kao under the name Quatarmin BTC 131.

Nonionic Surfactants

Examples of nonionic surfactants that may be used are described, forexample, in the Handbook of Surfactants by M. R. Porter, published byBlackie & Son (Glasgow and London), 1991, pp. 116-178, which isincorporated herein by reference in its entirety. The nonionicsurfactant may be alcohols, alpha-diols and (C₁-C₂₄)alkylphenols, thesecompounds being polyethoxylated, polypropoxylated and/orpolyglycerolated, and containing at least one fatty chain comprising,for example, from 8 to 18 carbon atoms, it being possible for the numberof ethylene oxide and/or propylene oxide groups to especially range from2 to 50, and for the number of glycerol groups to especially range from2 to 30.

Mention may also be made of copolymers of ethylene oxide and propyleneoxide, optionally oxyethylenated sorbitan fatty acid esters, sucrosefatty acid esters, polyoxyalkylenated fatty acid esters,polyoxyalkylenated fatty amides, optionally oxyalkylenatedalkyl(poly)glucosides, alkylglucoside esters, derivatives ofN-alkylglucamine and of N-acylmethylglucamine, aldobionamides, amineoxides and (poly)oxyalkylenated silicones.

The nonionic surfactants are more particularly chosen frommonooxyalkylenated or polyoxyalkylenated and monoglycerolated orpolyglycerolated nonionic surfactants, and alkyl(poly)glucosides. Theoxyalkylene units are more particularly oxyethylene or oxypropyleneunits, or a combination thereof, preferably oxyethylene units.

Useful nonionic surfactants may include: oxyalkylenated(C₈-C₂₄)alkylphenols; saturated or unsaturated, linear or branched,oxyalkylenated C₈-C₄₀ alcohols; saturated or unsaturated, linear orbranched, oxyalkylenated C₈-C₃₀ amides; esters of saturated orunsaturated, linear or branched, C₈-C₃₀ acids and of polyethyleneglycols; saturated or unsaturated, oxyethylenated plant oils;condensates of ethylene oxide and/or of propylene oxide, alone or asmixtures; oxyethylenated and/or oxypropylenated silicones; andalkyl(poly)glucosides.

As examples of monoglycerolated or polyglycerolated nonionicsurfactants, monoglycerolated or polyglycerolated C₈-C₄₀ alcohols areuseable. In particular, the monoglycerolated or polyglycerolated CC₈-C₄₀ alcohols correspond to formula (VIII) below:R₂₉O—[CH₂—CH(CH₂OH)—O]_(m)—H   (VIII)

in which formula (VIII):

R₂₉ represents a linear or branched C₈-C₄₀ and preferably C₈-C₃₀ alkylor alkenyl radical; and

m represents a number ranging from 1 to 30, or from 1 to 10.

As examples of compounds of formula (VIII), mention may be made oflauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleylalcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 OleylEther), oleyl alcohol containing 2 mol of glycerol (INCI name:Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol ofglycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetylalcohol containing 6 mol of glycerol, and octadecanol containing 6 molof glycerol.

The alcohol of formula (VIII) may represent a mixture of alcohols in thesame way that the value of m represents a statistical value, which meansthat, in a commercial product, several species of polyglycerolated fattyalcohols may coexist in the form of a mixture.

The alkyl(poly)glycoside nonionic surfactant(s) may be represented byformula (IX) below:R₃₀O—(R₃₁O)_(t)(G)_(v)   (IX)

in which:

R₃₀ represents a saturated or unsaturated, linear or branched alkylgroup comprising from about 8 to 24 carbon atoms, or an alkylphenylgroup in which the linear or branched alkyl group comprises from 8 to 24carbon atoms;

R₃₁ represents an alkylene group containing from about 2 to 4 carbonatoms,

G represents a saccharide unit comprising from 5 to 6 carbon atoms,

t denotes a value ranging from 0 to 10, or from 0 to 4, and

v denotes a value ranging from 1 to 15.

In some cases, the alkyl(poly)glycoside nonionic surfactant(s)correspond to formula (IX) in which:

R₃₀ denotes a linear or branched, saturated or unsaturated alkyl groupcontaining from 8 to 18 carbon atoms,

G denotes glucose, fructose or galactose, preferably glucose,

t denotes a value ranging from 0 to 3, and is preferably equal to 0, and

R₃₁ and v are as defined previously.

The degree of polymerization of the alkyl(poly)glucoside nonionicsurfactant(s), as represented, for example, by the index v in formula(IX), ranges on average from 1 to 15, or from 1 to 4. This degree ofpolymerization more particularly ranges from 1 to 2 and better stillfrom 1.1 to 1.5, on average.

The glycoside bonds between the saccharide units are of 1.6 or 1.4 typeand preferably of 1.4 type.

Examples of compounds of formula (IX) that may especially be mentionedare the products sold by the company Cognis under the names Plantaren®(600 CS/U, 1200 and 2000) or Plantacare® (818, 1200 and 2000). Use mayalso be made of the products sold by the company SEPPIC under the namesTriton CG 110 (or Oramix CG 110) and Triton CG 312 (or Oramix® NS 10),the products sold by the company BASF under the name Lutensol GD 70 orthe products sold by the company Chem Y under the name AG10 LK. Use mayalso be made, for example, of the 1,4-(C₈-C₁₆)alkylpolyglucoside as anaqueous solution at 53% by weight relative to the total weight of thesolution, sold by Cognis under the reference Plantacare 818 UP.

Amphoteric or Zwitterionic Surfactants

The amphoteric or zwitterionic surfactant that may be used incompositions according to the disclosure may be derivatives of aliphaticsecondary or tertiary amines, optionally quaternized, in whichderivatives the aliphatic group is a linear or branched chain comprisingfrom 8 to 22 carbon atoms, the amine derivatives containing at least oneanionic group, such as a carboxylate, sulfonate, sulfate, phosphate orphosphonate group. Mention may be made in particular of(C₈-C₂₀)alkylbetaines such as cocoylbetaine, sulfobetaines,(C₈-C₂₀)alkylamido(C₂-C₈)alkylbetaines such as cocoylamidopropylbetaineor (C₈-C₂₀)alkylamido(C₆-C₈)-alkylsulfobetaines, and mixtures thereof.

Among the derivatives of aliphatic secondary or tertiary amines,optionally quaternized, that may be used, as defined above, mention mayalso be made of the compounds of respective structures (I), (II) and(IIa) below:Ra—C(O)—NHCH₂CH₂—N⁺(Rb)(Rc)-CH₂COO⁻,M⁺,X⁻   (I)

in which formula (I):

Ra represents a C₁₀-C₃₀ alkyl or alkenyl group derived from an acidRa—COOH preferably present in hydrolysed coconut oil, or a heptyl, nonylor undecyl group; Rb represents a beta-hydroxyethyl group; and

Rc represents a carboxymethyl group;

M⁺ represents a cationic counterion derived from an alkali metal oralkaline-earth metal, such as sodium, an ammonium ion or an ion derivedfrom an organic amine; and

X⁻ represents an organic or mineral anionic counterion, such as thatchosen from halides, acetates, phosphates, nitrates, (C₁-C₄)alkylsulfates, (C₁-C₄)alkyl- or (C₁-C₄)alkylarylsulfonates, in particularmethyl sulfate and ethyl sulfate; or alternatively M⁺ and X⁻ are absent;Ra′—C(O)—NHCH₂CH₂—N(B)(B′)   (II)

in which formula (II):

B represents the group —CH₂—CH₂—O—X′;

B′ represents the group —(CH²)_(z)Y′, with z=1 or 2;

X′ represents the group —CH₂—COOH, CH₂—COOZ′, —CH₂CH₂—COOH or—CH₂CH₂—COOZ′, or a hydrogen atom;

Y′ represents the group —COOH, —COOZ′, CH₂CH(OH)SO₃H or the group—CH₂CH(OH)SO₃Z′;

Z′ represents a cationic counterion derived from an alkali metal oralkaline-earth metal, such as sodium, an ammonium ion or an ion derivedfrom an organic amine;

Ra′ represents a C₁₀-C₃₀ alkyl or alkenyl group of an acid Ra′—COOH,which may be coconut oil or in hydrolysed linseed oil, or an alkylgroup, especially a C₁₇ group and its iso form, or an unsaturated C₁₇group.

The compounds of this type are classified in the CTFA dictionary, 5thedition, 1993, under the names disodium cocoamphodiacetate, disodiumlauroamphodiacetate, disodium caprylamphodiacetate, disodiumcapryloamphodiacetate, disodium cocoamphodipropionate, disodiumlauroamphodipropionate, disodium caprylamphodipropionate, disodiumcapryloamphodipropionate, lauroamphodipropionic acid andcocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold bythe company Rhodia under the trade name Miranol C2M Concentrate and thecocoamphodipropionate sold by the company Evonik Goldschmidt under thetrade name Rewoteric AM KSF 40.Ra″—NH—CH(Y″)—(CH₂)_(n)—C(O)—NH—(CH₂)_(n′)—N(Rd)(Re)   (IIa)

in which formula (IIa):

Y″ represents the group —COOH, —COOZ″, —CH₂CH(OH)SO₃H or the group—CH₂CH(OH)SO₃Z″;

Rd and Re, independently of each other, represent a C₁-C₄ alkyl orhydroxyalkyl radical;

Z″ represents a cationic counterion derived from an alkali metal oralkaline-earth metal, such as sodium, an ammonium ion or an ion derivedfrom an organic amine;

Ra″ represents a C₁₀-C₃₀ alkyl or alkenyl group of an acid Ra″—COOH;

n and n′ denote, independently of each other, an integer ranging from 1to 3; and mixtures of these compounds.

Among the compounds of formula (IIa), mention may be made of thecompound classified in the CTFA dictionary under the name sodiumdiethylaminopropyl cocoaspartamide and sold by the company Chimex underthe name Chimexane HB. In some instances, the amphoteric or zwitterionicsurfactant(s) are chosen from cocoylbetaine, cocoylamidopropylbetaineand sodium cocoylamidoethyl-N-hydro xyethylaminopropionate.

The term “anionic surfactant” means a surfactant comprising, as ionic orionizable groups, only anionic groups. These anionic groups are chosenpreferably from the groups CO₂H, CO₂ ⁻, SO₃H, SO₃ ⁻, OSO₃H, OSO₃ ⁻O₂PO₂H, O₂PO₂H and O₂PO₂ ²⁻.

The anionic surfactant(s) that may be used may be alkyl sulfates, alkylether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates,monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates,alkylarylsulfonates, alpha-olefin sulfonates, paraffin sulfonates,alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamidesulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates,alkylsulfosuccinamates, acylisethionates and N-acyltaurates, salts ofalkyl monoesters and polyglycoside-polycarboxylic acids, acyllactylates,salts of D-galactoside uronic acids, salts of alkyl ether carboxylicacids, salts of alkyl aryl ether carboxylic acids, and salts ofalkylamido ether carboxylic acids; or the non-salified forms of all ofthese compounds, the alkyl and acyl groups of all of these compoundscontaining from 6 to 24 carbon atoms and the aryl group denoting aphenyl group. Some of these compounds may be oxyethylenated and thenpreferably comprise from 1 to 50 ethylene oxide units.

The salts of C₆-C₂₄ alkyl monoesters of polyglycoside-polycarboxylicacids may be chosen from C₆-C₂₄ alkyl polyglycoside-citrates, C₆-C₂₄alkyl polyglycoside-tartrates and C₆-C₂₄ alkyl polyglycoside-sulfosuccinates.

When the anionic surfactant(s) are in salt form, they may be chosenespecially from alkali metal salts such as the sodium or potassium saltand preferably the sodium salt, ammonium salts, amine salts and inparticular amino alcohol salts, or alkaline-earth metal salts such asthe magnesium salt.

Examples of amino alcohol salts that may especially be mentioned includemonoethanolamine, diethanolamine and triethanolamine salts,monoisopropanolamine, diisopropanolamine or triisopropanolamine salts,2-amino-2-methyl-1-propanol salts, 2-amino-2-methyl-1,3-propanediolsalts and tris(hydroxymethyl)aminomethane salts. Alkali metal oralkaline-earth metal salts and in particular the sodium or magnesiumsalts may be used.

Use is also made of (C₆-C₂₄)alkyl sulfates, (C₆-C₂₄)alkyl ethersulfates, which are optionally ethoxylated, comprising from 2 to 50ethylene oxide units, and mixtures thereof, in particular in the form ofalkali metal salts or alkaline-earth metal salts, ammonium salts oramino alcohol salts. More preferentially, the anionic surfactant(s) arechosen from (C₁₀-C₂₀)alkyl ether sulfates, and in particular sodiumlauryl ether sulfate containing 2.2 mol of ethylene oxide.

Oxidizing Agent

Oxidizing agents may be selected from, for example, peroxides,persulfates, perborates percarbonates, alkali metal bromates,ferricyanides, peroxygenated salts, or a mixture thereof. Oxidizingagents that may also be used include at least one redox enzyme such aslaccases, peroxidases, and 2-electron oxidoreductases, such as uricase,where appropriate in the presence of their respective donor orco-factor. Oxygen in the air may also be employed as an oxidizing agent.

In some cases, the oxidizing agent is hydrogen peroxide present in anaqueous solution whose titre may range from 1 to 40 volumes, such asfrom 5 to 40 volumes or such as from 5 to 20 volumes.

In other cases, the oxidizing agent is a persulfate and/or amonopersulfate such as, for example, potassium persulfate, sodiumpersulfate, ammonium persulfate, as well as mixtures thereof. In oneembodiment, the oxidizing agents in the present disclosure are selectedfrom hydrogen peroxide, potassium persulfate, sodium persulfate, andmixtures thereof. Hydrogen peroxide may commonly be used as theoxidizing agent.

In general, the oxidizing agent will be present in an amount of fromabout 0.05 to about 50% by weight, such as from about 0.1% to about 30%by weight, or such as from about 0.1% to about 20% by weight, or such asfrom about 1% to about 10% by weight, based on the total weight of theoxidizing composition.

In some instances, the oxidizing composition is aqueous or is in theform of an emulsion.

In other instances, the oxidizing composition is substantiallyanhydrous. The term “substantially anhydrous” means that the oxidizingcomposition is either completely free of water or contains noappreciable amount of water, for example, no more than 5% by weight, orno more than 2% by weight, or no more than 1% by weight, based on theweight of the oxidizing composition. It should be noted that this refersfor example to bound water, such as the water of crystallization of thesalts or traces of water absorbed by the raw materials used in thepreparation of the compositions according to the disclosure.

The oxidizing composition can contain at least one solvent, chosen fromwater, organic solvents, and mixtures thereof. When the oxidizingcomposition is substantially anhydrous, the oxidizing composition maycomprise at least one solvent chosen from organic solvents. Suitableorganic solvents for use in the oxidizing composition include ethanol,isopropyl alcohol, propanol, benzyl alcohol, phenyl ethyl alcohol,glycols and glycol ethers, such as propylene glycol, hexylene glycol,ethylene glycol monomethyl, monoethyl or monobutyl ether, propyleneglycol and its ethers, such as propylene glycol monomethyl ether,butylene glycol, dipropylene glycol, diethylene glycol alkyl ethers,such as diethylene glycol monoethyl ether and monobutyl ether, ethyleneglycol, propylene glycol, butylene glycol, hexylene glycol, propanediol, glycerin, hydrocarbons such as straight chain hydrocarbons,mineral oil, polybutene, hydrogenated polyisobutene, hydrogenatedpolydecene, polydecene, squalane, petrolatum, isoparaffins, andmixtures, thereof.

The organic solvent may, for example, be present in an amount rangingfrom about 0.5% to about 70% by weight, such as from about 2% to about60% by weight, preferably from about 5 to about 50% by weight, relativeto the total weight of the oxidizing composition.

The oxidizing composition may be in the form of a powder, gel, liquid,foam, lotion, cream, mousse, and emulsion.

The oxidizing composition of the present disclosure my also contain atleast one fatty substance as described above. Thus, the total amount offatty substances in the combination or mixture of the cosmetic andoxidizing compositions of the present disclosure may range from about10% to about 80% by weight, or such as from about 20% to about 60% byweight, or such as from about 20% to about 40% by weight, or such asfrom about 20% to about 30% by weight, based on the total weight of thecomposition.

Preservatives

One or more preservatives may be included in the compositions describedherein for treating hair. Suitable preservatives include, but are notlimited to, glycerin containing compounds (e.g., glycerin orethylhexylglycerin or phenoxyethanol), benzyl alcohol, parabens(methylparaben, ethylparaben, propylparaben, butylparaben,isobutylparaben, etc.), sodium benzoate, ethylenediamine-tetraaceticacid (EDTA), potassium sorbate, and/or grapefruit seed extract, orcombinations thereof. More than one preservative may be included in thecomposition. Other preservatives are known in the cosmetics industriesand include salicylic acid, DMDM Hydantoin, Formaldahyde, Chlorphenism,Triclosan, Imidazolidinyl Urea, Diazolidinyl Urea, Sorbic Acid,Methylisothiazolinone, Sodium Dehydroacetate, Dehydroacetic Acid,Quaternium-15, Stearalkonium Chloride, Zinc Pyrithione, SodiumMetabisulfite, 2-Bromo-2-Nitropropane, Chlorhexidine Digluconate,Polyaminopropyl biguanide, Benzalkonium Chloride, Sodium Sulfite, SodiumSalicylate, Citric Acid, Neem Oil, Essential Oils (various), LacticAcid, and Vitamin E (tocopherol).

The preservative is optionally included in an amount ranging from about0.01 wt. % to about 5 wt. %, about 0.15% to about 1 wt. %, or about 1wt. % to about 3 wt. %, based on the total weight of the composition.

Viscosity Modifying Agents

The compositions may contain one or more viscosity modifying agents,such as viscosity increasing agents. Classes of such agents include, butare not limited to, viscous liquids, such as polyethylene glycol,semisynthetic polymers, such as semisynthetic cellulose derivatives,synthetic polymers, such as carbomers, poloxamers, andpolyethyleneimines (e.g., PEI-10), naturally occurring polymers, such asacacia, tragacanth, alginates (e.g., sodium alginate), carrageenan,vegetable gums, such as xanthan gum, petroleum jelly, waxes, particulateassociate colloids, such as bentonite, colloidal silicon dioxide, andmicrocrystalline cellulose, surfactants, such as PPG-2 hydroxyethylcoco/isostearamide, emulsifiers, such as disteareth-75 IPDI, and salts,such as sodium chloride, and combinations thereof.

Forms

The compositions described herein may be in any suitable physical form.Suitable forms include, but are not limited to low to moderate viscosityliquids, lotions, milks, mousses, sprays, gels, creams, conditioners,and the like. Suitable excipients, such as those listed above, areincluded or excluded from the hair care formulation depending on theform of use of the formulation (e.g., hair spray, cream, conditioner,etc.).

i. Spray

The compositions described herein for treating hair may be in the formof a spray. The spray typically includes the composition comprising theone or more lactones and a cosmetically acceptable carrier. In someembodiments, the carrier is water or a water and alcohol mixture. Thespray formulation optionally includes an antioxidant, sunscreen agent,vitamin, protein, peptide, plant extract, humectant, oil, emollient,lubricant, thickener, hair conditioning agent, polymer, and/orsurfactant. Preferably, the spray formulation includes a preservative.In some embodiments, the formulation includes a fragrance. In somecases, the compositions described herein include a surfactant. In somecases, the compositions described herein contain water, fragrance, apreservative, and one or more lactones. In some cases, the compositionsdescribed herein contain water, fragrance, a preservative, and one ormore lactones. In some cases, the composition comprising one or morelactones contains water, a preservative, fragrance, the one or morelactones, and an anti-static agent. In some cases, the compositionsdescribed herein contain water, a preservative, fragrance, the one ormore lactones, and a hair conditioning agent. In some cases, thecompositions described herein contain water, a preservative, fragrance,the one or more lactones, and a surfactant.

The hair spray formulations may be dispensed from containers thatinclude aerosol dispensers or pump spray dispensers. Such dispensers areknown in the art and are commercially available from a variety ofmanufacturers.

When the hair spray formulation is dispensed from a pressurized aerosolcontainer, a propellant may be used to force the composition out of thecontainer.

Suitable propellants include, but are not limited to, a liquefiable gasor a halogenated propellant. Examples of suitable propellants includedimethyl ether and hydrocarbon propellants such as propane, n-butane,iso-butane, CFCs, and CFC-replacement propellants. The propellants maybe used singly or admixed.

The amount of propellant may range from about 10% to about 60% by weightof the formulation. The propellant may be separated from the hair repairformulation as in a two compartment container. Other suitable aerosoldispensers are those characterized by the propellant being compressedair, which can be filled into the dispenser using a pump or equivalentdevice prior to use. Conventional non-aerosol pump spray dispensers,i.e., atomizers, may also be used to apply the hair strengtheningformulation to the hair.

ii. Conditioners

The compositions disclosed herein for treatment of hair may be in theform of a conditioner. The conditioner typically includes thecomposition comprising the one or more lactones in a suitable carrier.Additionally, the conditioner may include cationic polymers derived frompolysaccharides, for example cationic cellulose derivatives, cationicstarch derivatives, cationic guar derivatives and cationic locust beangum derivatives, synthetic cationic polymers, mixtures or combinationsof these agents. The formulation may comprise other synthetic or naturalpolymers or polymers derived from biological preparation processes,which are functionalized, where appropriate, for example with cationicor neutral groups. These polymers may have a stabilizing orstrengthening action on the compositions, and/or a conditioning action(deposition on the surface of the skin or the hair).

iii. Creams

The compositions disclosed herein for treatment of hair may be in theform of a cream. The cream typically includes one or more lactones in asuitable carrier. The one or more lacatones may be included in anysuitable concentration. Typical concentrations of the one or morelactones in the cream range from small amounts such as approximatelyabout 0.01% (wt), at least 0.1% (wt), to large amounts, such as up toabout 50% (wt).

Implementation of the present disclosure is provided by way of thefollowing examples. The examples serve to illustrate the technologywithout being limiting in nature.

Examples

Normal bleached hair swatches (from IHIP, about 1.5 grams) were treatedand evaluated as set forth below.

Pre-Color Treatment: Normal bleached hair swatches were treated with apre-color treatment of 30 wt. % trisodium citrate (0.5 g solution/1 g ofhair). The solution was applied to the hair and allowed to stand for 20minutes at room temperature, then blown dry.Color Treatment Only: Hair swatches were colored using a commercial haircoloring product (1 g color creme/1.5 g developer/1 g hair) for 30minutes to give the hair an intense auburn color.In-Color Treatment: Hair swatches were colored using a commercial haircoloring product, in which a 30 wt. % solution of trisodium citrate wasadded (1 g solution of 30 wt. % trisodium citrate/1 g color creme/1.5 gdeveloper/1 g hair). The hair was processed for 30 minutes to give thehair an intense auburn color.Post-Color Treatment: The hair swatches were treated with a post-colortreatment of 30 wt. % citric acid (0.5 g solution/1 g of hair). Thetreated hair was allowed to stand at room temperature overnight.Hair Shampooing: The treated hair swatches were washed with an anionicshampoo (12% SLES, pH=5.5) 10 times. The hair swatch were blown dryafter each shampoo.Color Assessment: The L* and a* values of the hair swatches wereobtained before and after 10 shampoos. The higher the L* and the a*values, the lighter and redder the hair, respectively. The L*a*b*colorimetric system is a colorimetric system that assigns each color toa position in a spherical color space. In this color space, thebrightness is represented by a position in the ordinate (z-axis)direction, the hue is represented by a position in the circumferentialdirection, and the chroma is represented by a distance from the centeraxis. The position on the ordinate (z-axis) representing brightness isdesignated by L*, and the L* value changes from 0 corresponding to blackto 100 corresponding to white. The positive direction of the x-axiscorresponds to a red direction, the positive direction of the y-axiscorresponds to a yellow direction, the negative direction of the x-axiscorresponds to a green direction, the negative direction of the y-axiscorresponds to a blue direction, and the position on the x-axis isdesignated by a* of which value changes from −60 to +60 and the positionon the y-axis is designated by b* of which value changes from −60 to+60. The hue and chroma are represented by a* value and b* value,respectively.

The results of the various treatments described above are provided inthe table below.

L-Value a-Value Treatment Before After Before After No Treatment(control)* 25.3 32.7 16.3 18.7 Pre-color treatment using salt of 25.033.0 15.0 18.9 hydroxy-polycarboxylic acid (trisodium citrate) In-colortreatment using salt of 23.8 32.7 14.7 20.1 hydroxy-polycarboxylic acid(trisodium citrate) Post-color treatment using hydroxy- 27.5 31.5 22.120.4 polycarboxylic acid (citric acid) Pre-color treatment using salt of26.5 30.8 20.1 21.4 hydroxy-polycarboxylic acid (trisodium citrate) andpost-color treatment using hydroxy- polycarboxylic acid (citric acid)In-color treatment using salt of 27.4 30.4 22.6 21.7hydroxy-polycarboxylic acid (trisodium citrate) and in-color treatmentusing alkaline earth metal salt (CaCl₂)

As shown by the data in the tables above, the treatments with trisodiumcitrate provided better initial red color deposition but the color fadedafter 10 shampoos. The treatments with citric acid provided good initialredness (darkness), but the redness lightened after 10 shampoos.Treatments with both the trisodium citrate and the citric acid providedthe best results; the combination resulted in excellent initial colordeposition that was retained after 10 shampoos. Both the darkness andthe red hue were unexpectedly retained after 10 shampoos.

The terms “a,” “an,” and “the” are understood to encompass the plural aswell as the singular.

The expression “at least one” means “one or more” and vice versa, andthus includes individual components as well as mixtures/combinations.

The term “about” when referring to a value, is meant specifically that ameasurement can be rounded to the value using a standard convention forrounding numbers. For example, “about 1.5” is 1.45 to 1.54. All valuesset forth herein can be modified with the term “about,” if desired toimpart the meaning above, or recited without the term, regardless ofwhether the term “about” is specifically set forth (or is absent) inconjunction with any particular value in the specification.

All ranges and values disclosed herein are inclusive and combinable. Forexamples, any value or point described herein that falls within a rangedescribed herein can serve as a minimum or maximum value to derive asub-range, etc.

All publications and patent applications cited in this specification areherein incorporated by reference, and for any and all purposes, as ifeach individual publication or patent application were specifically andindividually indicated to be incorporated by reference. In the event ofan inconsistency between the present disclosure and any publications orpatent application incorporated herein by reference, the presentdisclosure controls.

The invention claimed is:
 1. A method for artificially coloring hair andinhibiting the coloring from fading, the method comprising: (a) treatinghair with a pre-color treatment composition comprising one or more saltsof a hydroxy-polycarboxylic acid; (b) treating the hair with a coloringcomposition; and (c) treating the hair with a post-color treatmentcomposition comprising one or more hydroxy-polycarboxylic acids; whereinthe hyroxy-polycarboxylic acid of the salt in (a) and in the post-colortreatment of (c) has the formula

wherein, x and y are independently 0 or 1; and t, u, v, and z areindependently 0 to
 3. 2. The method of claim 1, wherein the one or moresalts of the hydroxy-polycarboxylic acid of (a) are an alkali metalsalt, an alkaline earth metal salt, and/or a transition metal salt. 3.The method of claim 1, wherein the one or more salts of thehydroxy-polycarboxylic acid of (a) are salts of citric acid, tartaricacid, malic acid, 2-hydroxy malonic acid, 2-hydroxyl n-butyl1,2,4-tricarboxylic acid, glucaric acid, and/or 2-hydroxy n-butyl1,3,4-tricarboxylic acid.
 4. The method of claim 1, wherein the one ormore salts of the hydroxy-polycarboxylic acid of (a) comprises trisodiumcitrate.
 5. The method of claim 1, wherein the one or morehydroxy-polycarboxylic acids of (c) are selected from the groupconsisting of citric acid, tartaric acid, malic acid, 2-hydroxy malonicacid, 2-hydroxyl n-butyl 1,2,4-tricarboxylic acid, glucaric acid, and2-hydroxy n-butyl 1,3,4-tricarboxylic acid.
 6. The method of claim 1,wherein the one or more hydroxy-polycarboxylic acids of (c) comprisescitric acid.
 7. The method of claim 1, wherein the total amount of theone or more salts of the the hydroxy-polycarboxylic acid in thepre-color treatment composition of (a) are present in an amount of about1 wt. % to about 75 wt. %, based on the total weight of the pre-colortreatment composition; and the total amount of the one or morehydroxy-polycarboxylic acids in the post-color treatment composition of(c) are present in an amount of about 1 wt. % to about 75 wt. %, basedon the total weight of the post-color treatment composition.
 8. Themethod of claim 1, wherein the pre-treatment composition of (a) isapplied to the hair and allowed to remain on the hair for about 1 minuteto about 1 hour at a temperature of about 25° C. to about 45° C.; andthe post-treatment composition of (c) is applied to the hair withinabout 1 hour of the hair being artificially colored and is allowed toremain on the hair for about 1 minute to about 1 hour at a temperatureof about 20° C. to about 45° C.
 9. The method of claim 1, wherein thecoloring composition of (b) comprises one or more oxidative dyes.
 10. Akit comprising both a pre-color treatment composition and a coloringcomposition, as defined in claim 1.